Glyoxal-biscarbamate reaction products



United States Patent 3,341,550 GLYOXAL-BISCARBAMATE REACTION PRODUCTSSidney L. Vail and Clifford M. Moran, New Orleans, La.,

assignors to the United States of America as represented by theSecretary of Agriculture No Drawing. Original application Oct. 22, 1963,Ser. No. 318,129. Divided and this application Aug. 2, 1966, Ser. No.574,890

3 Claims. (Cl. 260309.7)

This application is a division of Serial No. 318,129, filed October 22,1963.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

In copending application Serial No. 170,848, filed February 2, 1962, nowPatent No. 3,111,522, of Sidney L. Vail, Clifford M. Moran, and Harry B.Moore, the formation and use of cy-clc compounds formed fromalkylenebis(carboxylic acid amides) and glyoxal were described. Thispresent invention has as an object the formation and use of a new classof compounds and their ethers having the general structure:

RC 6R wherein n is an integer of one or two, R is a member of the groupconsisting of an alkyl group of one to four carbon atoms, and R ishydrogen or alkyl group of one to four carbon atoms. These compoundscontain ester groups and hydroxyl groups or alkoxy groups which areuseful in crosslinking or other reactions requiring polyfunctionalreactants. In general, the compounds of the above structure shouldbeuseful as pesticides or in resin applications, textile finishing,pharmaceutical, and allied industries or as intermediates in thesefields.

The fiveand six-membered cyclic compounds of said Patent No. 3,111,522were prepared in relatively concentrated aqueous solutions. Thealkylenebis(carboxylic acid amides) were dissolved in a slightlyalkaline, aqueous solution containing about 15 to 30% glyoxal. Onstanding, the desired product generally crystallized from the solutionin a reasonable period of time.

In attempting this type of reaction with alkylenebiscarbamates it wasnoted that the biscarbamate failed to dissolve in the alkaline, aqueous30% glyoxal solution. In the case where the biscarbamate wasmethylenebis (methyl carbamate) a pasty mass was formed which onstanding became thicker. Solution of the mass in methanol, followed byfractional crystallization produced both the starting biscarbamate,methylenebis(methyl carbamate), and the desired compound, 1,3dicarbomethoxy-4,5-dihydroxyimidazolidine (I). The product as isolatedin this manner is contaminated by only a small amount of the unreactedbiscarbamate. Higher purity, if desired, is realized byrecrystallization from methanol.

The above reaction can be carried out in a methanol solution. Underthese conditions the methanolic solution is allowed to stand for a shortwhile and is then chilled to precipitate the starting bisc-arbamate, andthe desired product.

The reaction proceeds readily at room temperature (20 25 C.) andtemperatures of this order can be used. EX- cessive heating will causethe pH of the solution to decrease (presumably through the formation ofglycolic acid). Extremely acidic or basic conditions should be avoidedto minimize undesirable side reactions.

Ethers of the compounds of this invention can be formed by treating thecompounds with a slightly acidic, alcoholic solution. For example,1,3-dicarbomethoxy-4,5- dimethoxyimidazolidine (II) is prepared byheating the similar 4,5-dihydroxy compound (I) in an acidic methanolicsolution. Compound II was found to be more resistant to heat thanCompound I. Compound II on heating to 200 C. did not develop color,whereas Compound I developed color on melting at about C.

Another object of this invention relates to the treatment of cellulosictextile materials to produce textiles having improved properties. Ingeneral, it has been shown that N-methylol groups of amide typecompounds and their ethers are reactive with a variety of materials.Difunctional compounds of this type are known to readily form usefulpolymers and serve as effective crosslinking agents. Furthermore, theabsence of NH groups in the compounds of this invention decreases thepossibilities of chlorine retention and the subsequent disadvantages ofyellowing or scorch damage to the fabric.

More specifically, the fabrics produced in this invention are resistantto wrinkling, have improved resiliency, and possess wash-wearproperties. Moreover, the finishes produced from the new textiletreating agents of this invention were found to be extremely resistantto acid hydrolysis.

These and other objects of the invention are accomplished by treatingthe cellulosic textile with an aqueous solution containing one of thecompounds of this invention and an acidic catalyst. The concentration ofthe reactant can be varied depending on the particular textilefiuoborate, zinc nitrate, I magnesium chloride and citric acid areexamples of particularly suitable catalysts. From about 0.5% to about 5%by weight of the acidic catalyst is generally preferred.

Treatment of the cellulosic textile reacted materials.

The processes of substantially any hydrophilic fibrous cellulosicmaterial will be readily apparent to those skilled in the art. Forexample, a rapid cure at a relatively high temperature is generallyequivalent to a slower cure at a lower temperature. Rapid cures areoften used in industry.

In these examples all parts and percentages are by weight. The fabricswere tested by the following methods: Wrinkle recovery angle, Monsantomethod, American 0 Society for Testing Materials (ASTM) test D 1295-53T;

breaking strength, ASTM test D39-49; damage caused by retained chlorine,American Association of Textile Chemists and Colorists tentative testmethod 92-1958T.

Example I 4 1 Example 3 1,3 dicarbomethoxy 4,5 dihydroxyimidazolidine,described in Example 1, was dissolved in water. To serve as catalyst, toone-half of the solution an acid was added, while to the other half asubstance which produces acidity at elevated temperatures was added. Apiece of cotton fabric was immersed in each of the fractions, and theexcess liquid was removedmechanically. The wet fabrics were pinned to aframe, dried, and cured. The two setsof conditions are more fullydescribed in the table below:

Agent Con- Catalyst centration, Catalyst Concen- Drying Condi- CuringCondipercent trations, tions tions percent fl 60% Citric aCid-l-40% 2 60C./7 min 160 C./1 rnin.

MgCl fiHaO.

10 Zinc fluoborate 2 60 C./7 min 160 0J3 min.

about 8 with dilute sodium hydroxide. The thickened mass was dissolvedin warm methanol and then chilled to aid precipitation. Severalfractions of methylenebis(methylcarbamate) prepicipitated before thedesired product, 1,3- dicarbomethoxy-4,5-dihydroxyimidazolidine,precipitated. This product contained a small amount of methylenebis(methyl carbamate) which was essentially completely removed byrecrystallization of the product from methanol. The white,recrystallized product melted at 149-15 1 C. with a slight coloring andwas found to contain 38.21% carbon, 5.42% hydrogen, and 12.67% nitrogen.(Theory: 38.18% carbon, 5.49% hydrogen, and 12.72% nitrogen.)

The reaction was also carried out as follows: To 48.6 grams ofmethylenebis(methyl carbamate) was added 90.0 grams of 30% glyoxal whichhad been made slightly basic with sodium hydroxide. This mixture wasdissolved in 200 milliliters of methanol. The pH of the alcoholicsolution was about 9. After standing at 2025 C. for 20 hours thesolution was chilled and Worked up as before with similar results.

Example 2 To 3.5 grams of 1,3-dicarbomethoxy-4,5-dihydroxyimidazolidineprepared as described in Example 1 was added 40 milliliters of methanolwhich contained one drop of 6 N hydrochloric acid. The solution wasrefluxed for about six hours and then cooled. The desired product,1,3-dicarbomethoxy 4,5 dimethoxyimidazolidine, prepicitated and wasisolated by filtration. The white crystals melted at 100101 C. and theresultant liquid was not discolored when the temperature of the meltingpoint determination apparatus was raised to 200 C. The material wasfound to contain 43.48% carbon, 6.48% hydrogen, and 11.29% nitrogen.(Theory: 43.55% carbon, 6.50% hydrogen, and 11.29% nitrogen.)

The crease recovery angles of the treated fabrics were increased from29-39% over the untreated fabric. Further, these treated fabrics werenot yellowed by strong hypochlorite bleaching solutions. Chlorine damagein the scorch test was negligible. On heating the treated fabric in aurea-phosphoric acid stripping solution (30 min. at 80 C.), underconditions which essentially completely remove common finishes such asthose obtained from ureaformaldehyde, the crease recovery angle of thestripped fabric was not reduced and the nitrogen content of the fabricwas reduced only 10%.

We claim: 1. A compound represented by the formula 0 (0H2 n 0 ll Roou1TICOR H?-(."}H RO OR wherein n is an integer less than three, R is analkyl group of one to four carbon atoms, and R is hydrogen or an alkylgroup of one to four carbon atoms.

1,3-dicarbomethoxy-4,5-dihydroxyimidazolidine.

1 3-dicarbomethoxy-4,5-dimethoxyimidazolidine.

References Cited UNITED STATES PATENTS 2,717,896 9/1955 Goldman 260-2682,777,857 1/1957 Konig 260--309.7 3,029,164 4/1962 Seki et al 260-30973,111,522 11/1963 Vail et al 260-3097 3,112,156 11/1963 Vail et a1260-3097 FOREIGN PATENTS 783,051 9/1957 Great Britain.

WALTER A. MODANCE, Primary Examiner. N. TROUSOF, Assistant Examiner.

1. A COMPOUND REPRESENTED BY THE FORMULA